JPH03153787A - Curable coating composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having low toxicity and a high solid content and improved in the clarity of an appearance, curability under low humidity conditions, and impact resistance by mixing a silylated vinyl polymer, a specified organic compound, and a silanol-containing organopolysiloxane. CONSTITUTION:A silylated vinyl polymer (a) of a number-average molecular weight of at least 3,000, having a principal chain substantially consisting of a vinyl polymer chain and containing at least one Si atom bonded to a hydrolyzable group in the molecule at the end of the principal chain and/or on the side chain is obtained by, e.g. copolymerizing a macromonomer of a number- average molecular weight of 400 to 5,000, having both a C=C bond and a hydrolyzable silyl group in the molecule with a vinyl monomer. 10-99 pts.wt. component (a) is mixed with 1-90 pts.wt. organic compound (b) of a number-average molecular weight of 3,000 or lower, having at least one, preferably at least two, terminal Si atoms bonded to a hydrolyzable group and 1-500 pts.wt., based on 100 pts.wt. (a+b), silanol-containing organopolysiloxane (c) of a number- average molecular weight of 200 to 3,000, having at least one, preferably two to six, silanol groups on the average in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable composition for paint that is low in toxicity, high in solidity, and has improved appearance and curability.

More specifically, the present invention relates to a curable composition that is particularly useful as a top coating for automobiles.

[Problems to be solved by conventional technology/inventions] Conventionally, paint resins used for building exteriors, automobiles, industrial machinery, steel furniture, home appliances, plastics, etc. have mainly been made of alkyd melamine and acrylic. It is a melamine resin such as melamine or a two-component urethane resin.

Among these, melamine resins have problems in that harmful formalin is generated during curing, and the cured coating film has poor acid resistance and is susceptible to acid rain.

Furthermore, the toxicity of the isocyanate compounds used in two-component urethane resins is a problem.

In order to solve this problem, the present inventors have been studying vinyl polymers having a silicon atom (hydrolyzable silyl group) bonded to a hydrolyzable group for use in paints. As a result, it was discovered that this polymer solved the above problems and became a curable resin for paints with excellent weather resistance, and a patent application was previously filed (Japanese Unexamined Patent Application Publication No. 132977/1989, etc.).

On the other hand, there is a movement to regulate the total amount of solvents generated during the application of paints, such as the VOC Volatile Organic Substances (VOC) regulation in the United States, and there is a demand for high solids paints.

The vinyl polymer having a hydrolyzable silyl group is characterized in that the silyl group is hydrolyzed by moisture in the air and hardened through a condensation reaction. In addition, because it cures by forming stable siloxane bonds, it has superior chemical resistance and weather resistance compared to melamine resins such as acrylic melamine and alkyd melamine, or bifurcated urethane resins. be.

However, when this vinyl polymer having a hydrolyzable silyl group is used as a top coating for automobiles, there are the following four problems.

First, the appearance clarity, which is the most important aspect of an automotive top coating, is not always fully satisfactory.

Second, since the curing reaction is highly dependent on humidity, the curing reaction is slow under low humidity.

Thirdly, using this polymer alone, it is difficult to achieve a high solid state that satisfies the vOC regulations in the United States.

Fourthly, impact resistance is not necessarily sufficient as a top coating for automobiles.

[Means for Solving the Problems] The present inventors have made extensive studies to solve the above problems, and as a result, have completed the present invention.

That is, the present invention provides the following features: (A) The main chain consists essentially of a vinyl polymer chain, and at least one silicon atom in one molecule is bonded to a hydrolyzable group at the end of the main chain and/or at the side chain. Vinyl polymers with a number average molecular weight of 3,000 or more and a silyl glutinosity of 10~
99 parts (by weight, same hereinafter), (B) 1 to 90 parts of an organic compound having at least one silicon atom bonded to a hydrolyzable group in one molecule and having a number average molecular weight of less than 3000, and (C) The present invention relates to a curable composition for paints comprising 1 to 500 parts of a silanol-containing organopolysiloxane containing on average one or more silanol groups per molecule, based on 100 parts of the total amount of components (A) and (B).

[Example] The hydrolyzable silyl-absorbing vinyl polymer of component (A) in the present invention has a main chain substantially consisting of a vinyl polymer chain, and is hydrolyzed to the main chain terminal and/or side chain. It is a polymer having a small number (1, preferably 2 to 10) of silicon atoms bonded to a functional group in one molecule, and is generally obtained by copolymerization of a vinyl monomer and a hydrolyzable silyl group-containing monomer. may partially contain urethane bonds or siloxane bonds in the main chain or side chain.

The term "substantially consisting of a vinyl polymer chain" means that the properties of the resulting polymer mainly exhibit the properties of a vinyl polymer, and usually 60% of the units constituting the main chain
% or more, preferably about 8096 or more, consists of vinyl units.

The vinyl monomer is not particularly limited, and methyl (
meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, stearyl(meth)acrylate, benzyl(meth)acrylate, cyclohexyl(meth)acrylate, trifluoro Ethyl (meth)acrylate, pentafluoropropyl (meth)acrylate, unsaturated polycarboxylic acid (maleic acid, fumaric acid, itaconic acid, etc.) and carbon number 1
Unsaturated polycarboxylic acid esters such as diesters or half-esters with ~20 linear or branched alcohols; styrene, α-methylstyrene, chlorostyrene,
Aromatic hydrocarbon vinyl compounds such as styrene sulfonic acid, 4-hydroxystyrene, and vinyltoluene; Vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate; Vinyl compounds containing nitrile groups such as (meth)acrylonitrile; Epoxy group-containing vinyl compounds such as glycidyl (meth)acrylate; basic nitrogen-containing vinyl compounds such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, vinylpyridine, and aminoethyl vinyl ether; (meth)acrylamide, itaconic acid diamide, α-ethyl (meth)acrylamide,
Crotonamide, maleic diamide, fumaric diamide, N-vinylpyrrolidone, N-butoxymethyl(meth)acrylamide, N,N-dimethylacrylamide,
Amide glutinous vinyl compounds such as N-methylacrylamide and acryloylmorpholine; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth)acrylamide, Aronix 5700 ( Manufactured by Toagosei ■), Placel FA
-1, Placel FA-4, Placel P
Hydroxyl group-containing vinyl compounds such as H-1, Placel PH-4 (manufactured by Daicel Chemical); (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, and their salts (alkali metal salts, ammonium salts, amines) unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, their salts, acid anhydrides; vinyl methyl ether, vinyl chloride, vinylidene chloride, chlorobrene, propylene, butadiene, isoprene, maleimide, N-vinylimidazole and other vinyl compounds such as vinyl sulfonic acid.

The hydrolyzable silyl group-containing monomer may be, for example, - Mon'ena: % formula % (wherein R1 is a hydrogen atom or a monovalent hydrocarbon selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group). The group X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group.

(a is an integer of 0 to 2, and if each of X and R1 bonded to Sl is two or more, they may be the same group or different groups); Typical examples thereof include alkoxysilyl group-containing vinyl monomers.

Specific examples of the alkoxysilyl group-containing vinyl monomer (K) include l3CH2-CH3I (QC)+3)2, CH2-CH
31 (0CHz), 113 Betsu CH2-CllCOO (CH2)3 SI (OCHs
)2, CH2-CllCOO(C)12 )s 81
(OCRs ) 3, C) + 2- C CH3 Nobu (C) 13 ) COO (C) 12 ) 381 (QC2)
+5 )2, C)+2- CI-(CII2) 4-
91(OCHx)3, CH2-CI-(C112)
a -81(OCHx )3, CH2-C1(-0-(
C112) s -8l(QC)IJ )3, CH2
~CI+-0-C-(C112) Phantom-8l (QC)1
3) s.

1 Hs CH2-C(CH3)Coo(CIco)3Si
(OCH3)2, CH2-C(CH3)Coo(CH
2) 391 (OCH3)3, CH3 CH2-c-co+ CH2 1 )2 -O-(CH2)3-91 (OCHx )! ,C)+2
-C(CHs)Coo(C)12)$81(
QC2Hs)3, CI3C)lx = C-C-0-(CH2)1-5l(OCH3)J, and the like.

The above explanation relates to the case where component (A) in the present invention is produced from a relatively low molecular weight vinyl monomer and a hydrolyzable silyl group-containing monomer, but the impact resistance and solvent resistance of the coating film are In order to further improve the properties, it is preferable that the hydrolyzable silyl group-containing vinyl polymer of component (A) be obtained by copolymerizing the macromonomer (D) and the vinyl monomer (E).

The macromonomer (D) has both a carbon-carbon double bond and a hydrolyzable silyl group in one molecule, and has a number average molecular weight of 40 (I to 5000, preferably 500 to 4000).
Specifically, examples include structures such as the following.

R) S (wherein, R1 is a hydrogen atom or a monovalent hydrocarbon group selected from 1 to 10 carbon atoms, R↓ Re R9 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R4R6 is an alkyl group having 1 to 10 carbon atoms, 1O divalent alkyl group, aryl group or aralkyl group, R7 has 1 to 3 carbon atoms
0 alkyl group, aryl group, aralkyl group or (C
2R5O)3 S1+CH2+r-(CH30)3S
l+C)(2+r, X is a halogen atom, a hydrolyzable group selected from an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, and an amino group, Y
is -8- or -N-1O (where RIG is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), z is a polymethylene group, a polyether group, a polyester group, an organopolysiloxane group, a polyamide group, a polyurethane group a divalent organic group containing one or more organic groups selected from the group, a is an integer of 0 to 2,
(2) is an integer from 1 to 10, and g is an integer from 1 to lO).

Among macromonomers 01, those having about 1 to 30 1 -0-C-(CH2''rr groups in one molecule are preferable from the viewpoint of imparting flexibility to the coating film, and 1 -NH-C- It is preferable that the number of 0-groups is about 1 to 10 from the viewpoint of imparting solvent resistance to the coating film.

Methods for producing these macromonomers (D) include, for example, JP-A No. 88-1121105 and JP-A No. 6
Examples include the method described in Publication No. 3-112810.

Furthermore, the vinyl monomer (E) to be copolymerized with the macromonomer (D) is not particularly limited, and the above-mentioned vinyl monomer used to obtain the hydrolyzable silyl group-containing vinyl polymer of component (A) is It can be used as is.

Further, during copolymerization, the macromonomer (D) and the vinyl monomer (E) may be used in combination of IFJ or two or more from the above group.

The units from these hydrolyzable silyl group-containing vinyl monomers are contained in component (A) in an amount of 5 to 90% (wt%, the same applies hereinafter).
It is preferably included, and more preferably 11 to 70%.

As a method for producing a copolymer of a hydrolyzable silyl group-containing vinyl monomer and a vinyl monomer, for example,
Examples include the methods shown in 4-38395, 57-38109, and 5g-157810; solution polymerization using an azo radical initiator such as azobisisobutyronitrile; Most preferably, it is produced by.

In addition, if necessary, n-dodecylmercaptan, t-dodecylmercaptan, n-butylmercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyl Jetoxysilane, (CHIO)35t-8-9-
81(OCHs)3, (CHsO)3Sl-+C
HxhS-3-(CHz+r-31(OCHs))s
.

The molecular weight may be adjusted using a chain transfer agent such as (CHsO)3Sl-8s-81 (OCHJ If methoxysilane or the like is used, a hydrolyzable silyl group can be introduced at the end of the vinyl copolymer to be produced.

As the polymerization solvent used in the solution polymerization, hydrocarbons (
toluene, xylene, n-hexane, cyclohexane, etc.), acetic acid esters (ethyl acetate, butyl acetate, etc.)
, alcohols (methanol, ethanol, impropatol, n-butanol, etc.), ethers (ethyl cellosolve, butyl cellosolve, cellosolve acetate, etc.), ketones (methyl ethyl ketone, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone, Examples include non-reactive solvents such as acetone, etc., and there are no particular limitations as long as such solvents are used.

Regarding the molecular weight of component (A), if the molecular weight is made too low, the amount of non-crosslinked components will increase, so the number average molecular weight is 3000 or more,
Preferably, 3,000 to 10,000 are used.

The hydrolyzable silyl group-containing organic compound used in the present invention as component B) has the general formula: It is a compound containing at least one hydrolyzable silyl group represented by a monovalent hydrocarbon group selected from , aryl group, and aralkyl group, and the more it contains two or more silyl groups, the more crosslinking points there will be. It is valid. Further, it is preferable that the silyl group is present at the end of the molecule because it can participate in the crosslinking reaction more effectively.

Further, the number average molecular weight of the compound is preferably less than 3,000, and more preferably from 300 to 2,000. When the number average molecular weight is less than 300, volatility occurs and the solid content becomes <<
In other words, it becomes unsuitable for high solids production, and its impact resistance also decreases. Moreover, when the number average molecular weight is 3000 or more, the viscosity becomes high and it becomes difficult to make the curable composition for paint a high solid.

The amount of the hydrolyzable silyl group-containing organic compound of component (B) to be added is from lO to 10 of the silyl group-containing vinyl polymer of component (A).
99 parts, preferably 20 to 95 parts, 1 to 90 parts,
Preferably it is 5 to 80 parts. In addition, (A) component and (B
) The total amount of ingredients is 100 parts.

If the amount of component (B) added is less than 1 part, the viscosity of the curable composition for paint becomes high, making it difficult to achieve high solidity. On the other hand, if the amount added exceeds 90 parts, the appearance and initial drying properties will deteriorate.

Examples of such hydrolyzable silyl group-containing organic compounds include compounds represented by the following structural formula.

X5S1-R”-5IX3 (wherein, Rn is a divalent alkyl group having 1 to 30 carbon atoms, an aryl group, or an aralkyl group), X381 + CI2
"hO-R" -0÷CH2→TSIX3, -C)+2
0CNH(C)12)s SiX31 (CH2)s IX3
3, C113 X3 S 1+clI z+T-NII-C-0-E-
C1l 2CR2CIIcII 2C)12-I X3SI÷CHz'rrN CN 4 CHz-+
rSIXs, [X3 Sl + C112 size rgo r N
-CN + C1126) rsiXs These compounds have low viscosity and are therefore effective in making a curable paint composition high solid.

113 is also effective for impact resistance. These compounds may be used alone or in combination of two or more.

The silanol-containing organopolysiloxane which is the component (C) used in the present invention is a compound containing on average one or more silanol groups, preferably 2 to 6 on average, in one molecule. If the number of silanol groups is less than one per molecule, the effects of improving appearance and curability, which are the effects of the present invention, will be small. on the other hand,
If the number of silanol groups exceeds 6, the viscosity may become high and it may be difficult to achieve high solidity.

In addition, the number average molecular weight of component (C) is 200 or more and 3000 or more.
It is preferable that it is less than When the number average molecular weight is less than 200, volatility occurs, the solid content decreases, and the impact resistance also decreases. Furthermore, if the number average molecular weight is 3000 or more, the viscosity increases and it may be difficult to achieve high solidity.

Specific examples of such component (C) include TSR180, YR3113g manufactured by Toshiba Silicone ■, 5H8018 manufactured by Toray Silicone ■; KR- manufactured by Shin-Etsu Chemical ■.
211SKR-212, KR-214, KR-216 and the like. Among these, SR601g manufactured by Toray Silicone ■, which is a silanol-containing phenyl-substituted cyclic organopolysiloxane, and KR-
Compounds such as 218 improve the appearance of cured coatings, hardenability,
It is preferable because it has excellent solvent resistance.

Although it is not necessarily clear why the silanol-containing organopolysiloxane, component (C), improves the appearance and curability of cured coatings, the addition of component (C) improves the silanol groups of component (C). The hydrolyzable silyl groups of component (A) and component (B) undergo a direct condensation reaction and crosslinking reaction proceeds without undergoing a hydrolysis reaction that requires moisture, so the humidity dependence of the curing reaction is small. That, and as a result,
It is thought that the appearance is improved because the crosslinking reaction proceeds uniformly from inside the coating film.

The amount of component (C) added is 1 to 500 parts, preferably 5 to 20 parts, per 100 parts of the total of component (^) and component (B).
0 parts, more preferably 10 to 150 parts. (C)
If the amount of the component added is less than 1 part, the above-mentioned effect of improving the appearance and curability of the cured coating film will not be sufficient. Moreover, when it exceeds 500 parts, compatibility and impact resistance deteriorate.

Note that two or more types of such component (C) may be used in combination.

The composition of the present invention contains a hydrolyzable ester compound (F) as a dehydrating agent and an alkyl alcohol (
G) can be added.

Examples of the dehydrating agent (F) include ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, ethyl silicate, and methyl silicate, and hydrolyzable ester compounds such as methyltrimethoxysilane. Can be done. These dehydrating agents (F)
may be added during polymerization, or may be added after polymerization. The amounts added are (A) component, (B) component and (
It is preferably 100 parts or less, more preferably 50 parts or less, based on 100 parts of the solid content of component C).

Examples of the alkyl alcohol (6) as a solvent include alcohols in which the alkyl group has 1 to 10 carbon atoms; examples of such alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 5ee-butyl alcohol, te
rt-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, octyl alcohol, cellosolve, etc. are used.

There is no particular limitation on the amount of alcohol used, but (A
Solid content of component ), component (B) and component (C) * 10
0 parts, it is usually 100 parts or less, preferably 50 parts or less, and when using the solvent alone without using a dehydrating agent,
It is usually 0.5 to 100 parts, preferably 2 to 50 parts.

When the above-mentioned alcohol is used as the component (G) and is used in combination with the dehydrating agent, it is more stable in storage than when a composition consisting of the components (A), (B), and (C) is stored. performance is significantly improved. The amount of the solvent used that exhibits such effects varies depending on the molecular weight and composition of the solid component, component (B), and component (C) in the composition of the present invention, and although it cannot be generally specified, The solid content concentration, viscosity, etc. may be adjusted to a practically required value.

Although a curing catalyst (H) may be used in the composition of the present invention,
Examples of the curing catalyst (H) include organic tin compounds such as dibutyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dilarate, and tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, Monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate,
Phosphoric acids or phosphoric acid esters such as dibutyl phosphate, dioctyl phosphate, didecyl phosphate;
Propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, Cardura E manufactured by ■ Yuka Shell Epoxy ■ Addition reaction products of epoxy compounds such as Epicote 828 and Epicote 1001 manufactured by ■ with phosphoric acid and/or monoacidic phosphoric acid ester; organic titanate compounds; organic aluminum compounds; maleic acid , adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid,
Acidic compounds such as trimellitic acid, pyromellitic acid and their acid anhydrides, para-toluenesulfonic acid; amines such as hexylamine, di-2-ethylhexylamine, N,N-dimethyldodecylamine, dodecylamine; Reactants with acidic phosphate esters; examples include alkaline compounds such as sodium hydroxide and potassium hydroxide.

Among these curing catalysts (H), organic tin compounds, acidic phosphoric esters, reaction products of acidic phosphoric esters and amines, saturated or unsaturated polyhydric carboxylic acids or their acid anhydrides, reactive silicon compounds, organic titanates A compound, an organoaluminum compound, or a mixture thereof is preferred because of its high activity.

Such curing catalysts (H) may be used alone or in combination of two or more.

There is no particular limitation on the amount of component (H) used, but it is usually 0.05 to 20 parts, preferably 0.05 parts per 100 parts of solid content of component (A), component (B), and component (C). ~1
It is 0 copies. When the amount of component (H) used is less than 0.05 parts, curability tends to decrease, and when it exceeds 20 parts, the appearance of the coating film tends to decrease.

Furthermore, when used as a top coat, by adding an ultraviolet absorber (I) and a light stabilizer (C),
- The layer weather resistance can be improved.

As the ultraviolet absorber (I), a wide variety of conventionally known ones can be used, and for example, benzophenone-based, triazole-based, phenyl salicylate-based, diphenyl acrylate-based, acetophenone-based ultraviolet absorbers are preferred.

As the light stabilizer (J), a wide variety of conventionally known ones can be used, such as bis(2,2,8,6-tetramethyl-
4-piperidyl) sebacate, bis(I゜2.2.8.
6-bentamethyl-4-piperidyl) sebacate, 2-
(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(I,2,2°8
．． 6-bentamethyl-4-piperidyl), tetrakis (
2,2,8,6-tetramethyl-4-piperidyl)-1
, 2,3,4-butanetetracarboxylate, and tetrakis(I,2,2,6,8-pentamethyl-4-piperidyl')-1,2,3,4-butanetetracarboxylate. These may be used alone,
2P! The above may be used in combination.

By using a UV absorber and a light stabilizer together in the top coat clear paint, weather resistance can be further improved.

The blending amount of the ultraviolet absorber is usually 0.1 to 10 parts per 100 parts of the solid molecule fi of the top coat clear paint.
Preferably it is 1 to 5 parts. In addition, the amount of light stabilizer is
For 100 parts of solid content of top coat clear paint,
It is usually 0.1 to 10 parts, preferably 1 to 5 parts.

Additionally, top coat clear paints contain additives such as diluents, anti-cissing agents, and leveling agents depending on the application; cellulose compounds such as nitrocellulose and cellulose acetate butyrate; epoxy resins, melamine resins, and vinyl chloride resins. , chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, and other resins may be added.

There are no particular limitations on the method for preparing the top coat clear paint consisting of the above ingredients, but for example, (^) ingredients,
(B) component and (C) component are cold blended, or (A) component, (B) component and (C) component are mixed and then heated (hot blend) to cause a partial reaction. It is prepared by mixing with component H).

Next, the composition of the present invention will be explained based on Examples.

Synthesis example 1 A mixed solution of parts 1-1 to 4 below was prepared.

Part 1-1 Styrene (hereinafter referred to as ST) 13g Methyl methacrylate (hereinafter referred to as HMA)
) (hereinafter referred to as TSMA) 18g butyl acrylate (hereinafter referred to as BA) 34 γ-trintoxysilylpropylmercabutane (hereinafter referred to as TSSH)
3g methyl alcohol (hereinafter referred to as MeOH) 2g 2.2°-azobisisobutyronitrile (hereinafter referred to as
(referred to as AIBN) 4g - Mixed solution g of butyl acetate (hereinafter referred to as BuAc) Part 2 BuAc 14g xylene 10g mixed solution Part 3 AION O, 4g
BuAc Log mixed solution part 4 Methyl orthoacetate (hereinafter referred to as MOA) 4gMeOH
4 g of mixed solution Under a nitrogen atmosphere, the mixed solution of Part 1-1 was added dropwise at a constant speed over 5 hours into the mixed solution of Part 2 heated to 110°C. Next, the mixed solution of Part 3 was added dropwise into the solution at a constant speed over a period of 1 hour. After that, continue at 110℃ for 2
After stirring for an hour, the mixture was cooled to room temperature. Finally, the mixed solution of Part 4 was added and stirred.

The solid content concentration of the resulting solution was 64%.

Further, when the obtained compound was analyzed by GPC, the number average molecular weight was 3,500.

Synthesis example 2 A mixed solution of parts 1-2 to 4 below was prepared.

Part 1-2 Macromonomer T MA SMA B^ 5311 eOII AION 1g 3g 8g 9g 9g 9g 9g 9g BuAc
8 g mixed solution portion 2 BuAc 14 g xylene Log mixed solution portion 3 AION 0.4 gB
uAc 1G g mixed solution portion 4 MoA 4 gM
Mixed solution of 4 g of eOH Under a nitrogen atmosphere, the mixed solution of Part 1-2 was added dropwise at a constant speed over 5 hours into the mixed solution of Part 2 heated to 110°C. Next, the mixed solution of Part 3 was added dropwise into the solution at a constant speed over a period of 1 hour. After that, continue at 110℃ for 2
After stirring for an hour, the mixture was cooled to room temperature. Finally part 4
A mixed solution of was added and stirred.

The resulting solution had a solid content concentration of 65%.

Further, when the obtained compound was analyzed by GPC, the number average molecular weight was 4100.

Example 1 (I) (Al) Polymer obtained in Synthesis Example 1 75
Part (B1) 15 parts of a compound represented by the following formula (CI
) KR-216 (silanol-containing organopolysiloxane manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts (B2) (
C) 130) 381 (C112)Ill 5l(O
CH3) 3 (KBM310B manufactured by Shin-Etsu Chemical JI#)
$1970 (manufactured by Kusumoto Kasei) 0.3% as a leveling agent for total solids of 10 parts or more; curing catalyst ■
As a mixture, 3% of a mixture of DP-8 (dioctylphosphate) (manufactured by Masudai Chemical Industry Co., Ltd.) / Firmin DM20 (N,N-dimethyldodecylamine) (manufactured by Kao Corporation) -1/1 (weight ratio) was added. added.

This mixture was diluted with Tsurpetz Mist 100 (aromatic high boiling point solvent) (manufactured by Exxon Chemical Co., Ltd.) and poured into a Ford cup.
It was adjusted to a viscosity of 5 to 20 seconds and used as a clear paint for top coat.

(I) Synthesis example 1 used as the (A1) component of [+]
Instead of the obtained polymer, use the same amount of the polymer obtained in Synthesis Example 2.
There was m. A clear paint for top coat was prepared in the same manner as in (I) in other respects.

The following coatings were performed using the paints prepared in (I) and (I), respectively, and the coating films were evaluated by the following method. The results are shown in Table 1.

A coated mild steel plate that had been degreased and treated with phosphoric acid was coated with an automotive epoxyamide-based cationic electrodeposition primer and an intermediate coat surfacer as a test piece, and then a commercially available acrylic melamine resin paint (Silver Metallic Space) was applied as a base coat. did. Next, the top coat clear paint prepared in (I) and (I) above was applied wet-on-wet, and after setting for 20 minutes, it was baked at 120°C for 30 minutes.

The dry film thickness was approximately Loans for the base coat and approximately 50 JA for the clear top coat.

(DuPont impact strength) Using a 1/2 inch striking core, determine the highest value without any abnormality observed in the coating film.

(Rubbing property)) Soak 4EK (methyl ethyl ketone) in absorbent cotton,
Each test plate is rubbed 200 times under the same conditions. Thereafter, the surface condition was observed and evaluated as ◎ if there was no change, 0 if there were some scratches on the surface, and × if poor.

Comparative Example 1 1 Polymer obtained in Synthesis Example 1 as the (AI) component in place of the total of 120 parts of the (AI) component, (Bl) component, (C1) component, and (B2) component in (I) of Example 1 A clear paint for top coat was prepared in the same manner as in (I) except that 100 parts was used. The obtained paint was evaluated in the same manner as in Example 1. The results are shown in Table 1.

It turns out that it is good.

Synthesis example 3 A mixed solution of parts 1-3 below was prepared.

Part ta Macromonomer Table 1 From the results in Table 1, the solvent resistance of component (A) produced using a macromonomer is better. T MA 5MA 2-Ethylhexyl methacrylate 3g 1g 9g 7r TSSH3g MeOH2g AIBN
4gBuAc
The reaction was carried out in the same manner as in Synthesis Example 2, except that 8 g of the mixed solution portion 1-3 was used.

The solid content concentration of the resulting solution was 65%.

Further, when the obtained compound was analyzed by GPC, the number average molecular weight was 4,200.

It was diluted with Tsurupetz 5too to make the solid content concentration 60%.

Examples 2 to 6 and Comparative Examples 2 to 3 The polymer obtained in Synthesis Example 3 was blended into the composition shown in Table 2 to prepare a clear paint for top coat.

The obtained paint was evaluated in the same manner as in Example 1.

The results are shown in Table 2.

In addition, at this time, painting, setting, baking, and evaluation are
All absolute humidity is O, 01vt/vt (ghHz O/
kg dry air). In addition, pencil hardness, surface gloss, and appearance were evaluated using the following methods.

Furthermore, (B3) in Table 2 is a compound represented by the formula;
is a silanol-containing phenyl-substituted cyclic organopolysiloxane manufactured by Toray Silicone (1), and KR-212 is a silanol-containing organopolysiloxane manufactured by Shin-Etsu Chemical (2).

(Pencil hardness) Measured in accordance with JIS K 540G.

(Surface Glossiness) 8011 specular reflectance was measured in accordance with JIS K 5400.

(Appearance) A comprehensive evaluation of luster and texture was made by visual inspection.

◎＞0＞＠＞Δ〉× indicates good, slightly good, fair, slightly poor, and poor.

[Margin below] From the results in Table 2, in order to obtain a non-solid paint with good appearance, components (A), (B), and (C) are required.
It can be seen that three components are essential. In other words, Comparative Example 2 does not contain component (B), resulting in high viscosity and cannot be made into a high solid paint, while Comparative Example 3 does not contain component (C).
Since it does not contain any ingredients, it has poor appearance.

Example 7 and Comparative Example 4 Using the coating compositions used in Example 3 and Comparative Example 3,
Absolute humidity is 0.001 for everything from painting to evaluation.
It was conducted and evaluated under a vt/vt environment. The results are shown in Table 3.

From the results in Table 3, it can be seen that the composition of Comparative Example 3, which does not contain component (C), is easily affected by humidity, and when cured under low humidity conditions, the physical properties deteriorate due to poor curing.

[Effects of the Invention] The composition of the present invention is high solid and has improved curability, and the formed coating film has good appearance.

Table 3 Procedural amendments stamped) December 12, 1990 5. Subject of amendment (I) "Claims" column of the description (2) "Detailed description of the invention" column 1 of the description Display of the case 1999 Patent Application No. 293177 2 Name of the invention Curable composition for paint 3 Person making the amendment Relationship to the case Patent applicant Address 3-2-4 Nakanoshima, Kita-ku, Osaka Name Name
(094) Kanebuchi Chemical Industry Co., Ltd. Address: 2-2-22 Tanimachi, Chuo-ku, Osaka: Contents of the 6th layer amendment ” shall be corrected as follows.

(2) "In one molecule" on page 6, lines 13-14 of the specification is corrected to "terminal of the molecule."

(3) “Aronics...” on page 9, lines 14-16.
l'M-4J is "Aronix 5700 manufactured by Kagaku Kogyo Co., Ltd.", Placcol FA-1 (caprolactone acrylate (rrri), Placce
l, I'A-4 (polycaprolactone acrylate (
n-4)), I'1accel FM-1 (caprolactone methacrylate (n-1)), Placel
FM-4 (polycaprolactone acrylate (tr4)
) Correct as J.

r R1 (4) Same page 10, line 10 (7) X3. -5l-Jwo (5) On page 15, line 12, the "polyester group" is corrected to "polyester group such as caprolactone, methylvalerolactone, etc."

"0 1 ((6) -0 -C-(CH2+-J) on the last line of page 15 is corrected to "0 1 caprolactone (-0-C-+CHz→-1)".

(7) On page 19, lines 5-6, "at least one" is corrected to "at least one at the end of the molecule."

(8) Correct "2 or more" in line 7 of page 19 to "2 or more at the end of the molecule."

(9) On page 19, lines 8-10, “At the end of the molecule...
preferable. ” to “It is better to exist at the end of the molecule than in the side chain (
It undergoes a faster integrated reaction with the silanol group of component C) and can effectively participate in the crosslinking reaction, resulting in better curability of the composition of the present invention. ” he corrected.

7 List of Attached Documents (I) Amended Claims 1 Amended Claim rl (A) The main chain consists essentially of a vinyl polymer chain, and the main chain terminal and/or side 10 to 99 parts by weight of a silyl group-containing vinyl polymer having at least one silicon atom bonded to a hydrolyzable group in its chain and having a number average molecular weight of 3,000 or more; (B) a hydrolyzable group; 1 to 90 parts by weight of an organic compound having at least one bonded silicon atom at the terminal of U and a number average molecular weight of less than 3000, and the total amount of components (C) (^) and (B) 100ff
Silanol-containing organopolysiloxanes 1 to 5 containing on average one or more silanol groups per molecule per i weight part
00ff! A curable composition for paint consisting of parts by weight.

The hydrolyzable silyl lA-containing vinyl polymer that is component 2 (A) has both carbon-carbon double viscosity and a hydrolyzable silyl group in one molecule, and has a number average molecular weight of 400 to 5000.
Macro-septumer (0) and vinyl monomer (E
2. The composition according to claim 1, which is a copolymer with ).

The hydrolyzable silyl group-containing organic compound that is component 3 (B) has a silicon atom bonded to a hydrolyzable group at the end of the molecule.
The composition according to claim 1, comprising at least one.

2. The composition according to claim 1, wherein the silanol-containing organopolysiloxane as component 4(C) has an average of 2 to 6 silanol groups in one molecule and a number average molecular weight of 200 to 3,000.

2. The composition according to claim 1, wherein the silanol-containing organopolysiloxane as component 5(C) is a phenyl-substituted cyclic organopolysiloxane.

6 Furthermore, a hydrolyzable ester compound as a dehydrating agent (
2. A composition according to claim 1, comprising F) and an alkyl alcohol (G) as a solvent.

7. The composition according to claim 1, further comprising a curing catalyst (H).

8. The composition according to claim 1, further comprising a UV absorber (summer) and/or a light stabilizer (J).

9. The composition according to claim 2, wherein the macromonomer (D) contains a 1÷0-C-(CH2)S÷ group in the molecule.

(2) The composition according to claim 2, wherein the macromonomer (D) contains a urethane bond in the molecule. "that's all

Claims (1)

[Scope of Claims] 1 (A) The main chain consists essentially of a vinyl polymer chain,
Silyl group-containing vinyl polymer having at least one silicon atom bonded to a hydrolyzable group at the end of the main chain and/or side chain in one molecule and having a number average molecular weight of 3000 or more 1
0 to 99 parts by weight, (B) 1 to 90 parts by weight of an organic compound having at least one silicon atom in one molecule bonded to a hydrolyzable group and having a number average molecular weight of less than 3000, and (C) (A) 1 to 500 silanol-containing organopolysiloxanes containing an average of one or more silanol groups per molecule, based on 100 parts by weight of the total amount of components and (B).
A curable composition for paint consisting of parts by weight. 2. The hydrolyzable silyl group-containing vinyl polymer as component (A) has a carbon-carbon double bond and a hydrolyzable silyl group in one molecule, and has a number average molecular weight of 400 to 5000.
Macromonomer (D) which is, and vinyl monomer (E
2. The composition according to claim 1, which is a copolymer with ). 3. The composition according to claim 1, wherein the hydrolyzable silyl group-containing organic compound as component (B) contains two or more silicon atoms bonded to a hydrolyzable group in one molecule. 4. Component (C), the silanol-containing organopolysiloxane, has an average of 2 to 6 silanol groups in one molecule, and has a number average molecular weight of 200 to 3,000.
Compositions as described. 5. The composition according to claim 1, wherein the silanol-containing organopolysiloxane as component (C) is a phenyl-substituted cyclic organopolysiloxane. 6 Furthermore, a hydrolyzable ester compound as a dehydrating agent (
2. A composition according to claim 1, comprising F) and an alkyl alcohol (G) as a solvent. 7. The composition according to claim 1, further comprising a curing catalyst (H). 8. The composition according to claim 1, further comprising an ultraviolet absorber (I) and/or a light stabilizer (J). 9. The composition according to claim 2, wherein the macromonomer (D) contains a ▼ group having a mathematical formula, a chemical formula, a table, etc. in the molecule. 10. The composition according to claim 2, wherein the macromonomer (D) contains a urethane bond in the molecule.